Gels derived from extending grafted centipede polymers and polypropylene

ABSTRACT

The present invention teaches a method for enabling the formation of a high damping, soft polymer gel. The method includes: reacting a poly(alkenyl benzene-co-maleimide) polymer with a maleated polyalkylene and an alkyl diamine under substantially dry conditions sufficient to form a polyalkylene grafted poly(alkenyl benzene-co-maleimide) polymer product; and, dispersing the polyalkylene grafted poly(alkenyl benzene-co-maleimide) polymer product with an extender oil sufficient to form the gel. The present invention also contemplates a polymer gel composition, a polymer composition and an article manufactured from the polymer gel composition.

FIELD OF THE INVENTION

This applicatioin is a continuation of U.S. patent application Ser. No.09/073,735, filed May 6, 1998 now U.S. Pat. No. 6,248,825.

BACKGROUND OF THE INVENTION

The polymerization of styrene and maleic anhydride by free radicalinitiation is well known in the prior art. Similarly,poly(styrene-co-maleic anhydride) polymer is well known. Further,imidization between a maleic anhydride and a primary amine group is acommonly known chemical reaction. Patent publications which haverecognized these reactions include: German Patent DE 4241538, assignedto Leuna-Werke A.-G; Japanese Patent JP 94248017, assigned to MonsantoKasel Kk.; and, Italian Patent EP 322905 A2, assigned to MontedipeS.p.A. Various other non-patent publications have also recognized thesereactions. Included among them are: L. E. Colleman, Jr., J. F. Bork, andH. Donn, Jr., J. Org. Chem., 24, 185(1959); A. Matsumoto, Y. Oki, and T.Otsu, Polymer J., 23 (3), 201(1991); L. Haeussler, U. Wienhold, V.Albricht, and S. Zschoche, Themochim. Acta, 277, 14(1966); W. Kim, andK. Seo, Macromol. Rapid Commun., 17, 835(1996); W. Lee, and G. Hwong, J.Appl. Polym. Sci., 59, 599(1996); and, I. Vermeesch and G. Groeninckx,J. Appl. Polym. Sci., 53, 1356(1994).

The synthesis of monofunctional N-alkyl and N-aryl maleimides are alsowell known in the prior art. They have been extensively used to improvethe heat stability of homo- and especially copolymers prepared fromvinyl monomers. Typically, the bulk resins comprise ABS(poly(acrylonitrile-co-butadiene-co-styrene)) or a polyblend ofpoly(acrylonitrile-co-butadiene) and poly(styrene-co-acrylonitrile); PVC(poly(vinyl chloride)); SAN (poly(styrene-co-acrylonitrile)); PMMA(poly-(methyl methacrylate)); and the like. The maleimides can becopolymerized with other monomers such as acrylonitrile, butadiene,styrene, methyl methacrylate, vinyl chloride, vinyl acetate and manyother comonomers. A more preferred practice in the industry is toproduce copolymers of maleimides with other monomers such as styrene andoptionally acrylonitrile and to blend these with ABS and SAN resins. Inany event, the polymer compositions are adjusted so that the copolymersare fully compatible with the bulk resins (e.g., ABS and/or SAN) asshown by the presence of a single glass transition point (T(g)) asdetermined by differential scanning calorimetry (DSC).

It has long been recognized that two or more polymers may be blendedtogether to form a wide variety of random or structured morphologies toobtain products that potentially offer desirable combinations ofcharacteristics. However, it may be difficult or even impossible inpractice to achieve many potential combinations through simple blendingbecause of some inherent and fundamental problem. Frequently, the twopolymers are thermodynamically immiscible, which precludes generating atruly homogeneous product. This immiscibility may not be a problem sinceoften it is desirable to have a two-phase structure. However, thesituation at the interface between these two phases very often does leadto problems. The typical case is one of high interfacial tension andpoor adhesion between the two phases. This interfacial tensioncontributes, along with high viscosities, to the inherent difficulty ofimparting the desired degree of dispersion to random mixtures and totheir subsequent lack of stability, giving rise to gross separation orstratification during later processing or use. Poor adhesion leads, inpart, to the very weak and brittle mechanical behavior often observed indispersed blends and may render some highly structured morphologiesimpossible.

It is particularly desirable to prepare a grafted copolymer having theimpact strength of polypropylene and the elastomeric properties of ablock copolymer. It is also desireable to add an extender or plasticizerto the resultant grafted copolymer in order to obtain a copolymer havinga low Shore A hardness.

OBJECTS OF THE INVENTION

Accordingly, it is an object of this invention to provide an oil or lowmolecular weight component extended grafted “centipede” polymer of amaleated polypropylene and a poly(alkenyl benzene-co-maleimide) that isuseful in producing high damping and soft materials.

More specifically, it is an object of this invention to provide agrafted centipede polymer formed by reacting maleated polypropylene anda poly(alkenyl benzene-co-maleimide) with a diamine.

Another object of the invention is to provide oil or low molecularweight component extended grafted centipede polymers that exhibitimproved properties, including low Shore A hardness less than 35, highdamping properties and a service temperature of about 100° C.

SUMMARY OF THE INVENTION

The present invention is directed to an oil or low molecular weightcomponent extended grafted poly(alkenylbenzene-co-maleimide)-polypropylene polymer soft gel composition havingdamping properties useful in producing molded products having heatresistance and a high elasticity and damping property.

The present invention is broadly directed to grafted polymercompositions of a maleated polypropylene and a poly(alkenylbenzene-co-maleimide) reacted with a diamine. It is further directed toa process for preparing an oil extended grafted polymer compositionsbroadly comprising a maleated polypropylene grafted to a functionalizedthermoplastic material, namely a poly(alkenyl benzene-co-maleimide),under conditions sufficient to permit grafting of the functionalizedpolypropylene with the functionalized thermoplastic material. Thegrafted polymer is a glass-like material that becomes a soft andrubber-like elastomer after being oil-extended.

DETAILED DESCRIPTION OF THE INVENTION

The extended grafted polymer gels of the present invention contain: 100parts by weight of a grafted polymer of a poly(alkenylbenzene-co-maleimide) having at least one maleated polypropylenesegments grafted thereto through the at least one functional linkageformed by a crosslinking reaction with a diamine grafting agent; and atleast 30, preferably 30 to 1000, parts by weight of an extender such asan oil or a low molecular weight component. The poly(alkenylbenzene-co-maleimide) is a “centipede” polymer formed by imidizing apoly(alkenyl benzene-co-maleic anhydride) with a primary amine. The“centipede” polymer has a high molecular weight spine connected withmany relatively short side chains formed from the addition of theprimary amines. The length of the main chain usually equals or is longerthan the entanglement length, which is herein defined theoretically asan order of magnitude of 100 repeating units, while the length of theside chains is much smaller than the entanglement length.

The preferred alkenyl benzenes contributed monomer units of thepoly(alkenyl benzene-co-maleimide) “centipede” polymer are eitherstyrene or alpha-methylstyrene. The terms “alkenyl benzene” and “vinylaromatic” are understood to be interchangeable as used herein.

The poly(alkenyl benzene-co-maleimide) described herein are subsequentlygraft-reacted through a difunctional linking or grafting agent to amaleated polypropylene to yield a grafted polymer having at least onepolypropylene segment grafted thereto through the at least onefunctional linkages thus formed.

The maleated polypropylene may be any of the conventionally knownpolypropylene compounds that are subsequently maleated by methods knownin the art. The polypropylene grafted segment or segments have molecularweights “M_(w)” of about 10,000 up to about 10,000,000, or higher,preferably about 20,000 to about 300,000.

The crystallinity, or tacticity, of the polypropylene may vary frombeing substantially amorphous to being completely crystalline, that isfrom about 10-100% crystallinity. Most typically, because of theextensive commercial use of isotactic polypropylene, the graftedpolypropylene will be substantially crystalline, e.g., greater thanabout 90%. Generally, the polypropylene is substantially free ofethylene. However, under certain circumstances small amounts ofethylene, on the order of less than about 10% by weight, may beincorporated. Furthermore, in certain instances the polypropylenecontain small amounts of ethylene in copolymers known as “reactorcopolymers”. Thus, it is within the scope of the invention that thegrafted polypropylene contain minor amounts of ethylene, both as part ofethylene-propylene segments and as polyethylene segments.

Polymerization conditions for the preparation of polypropylene are wellknown in the art. Propylene can be polymerized into isotacticpolypropylene in the presence of stereo-specific Ziegler-Natta catalystsystems comprising compounds of the transition metals of Groups 4 to 6and 8 of the Periodic Table of elements, preferably titanium compounds,most preferably titanium halides, and organometallic compounds ofelements of groups 1 to 3 of the Periodic Table, especially aluminumalkyls or aluminum alkyl halides. Illustrative examples include titaniumtrichloride, titanium tetrachloride as catalysts and triethylaluminumand diethyl aluminum chloride as cocatalysts. These transition metalcatalyst systems can be non-supported or supported, for example, silicagel, or metal oxides and dihalides, such as MgO, MgCl₂, ZnCl₂, etc. Suchsystems can be reacted together and can be complexed with a variety ofLewis-base electron donors.

Molecular weight control is typically achieved by the incorporation ofhydrogen via a feed stream into the polymerization reactor. The hydrogenis added at about 0 to 30 mole % based on the total monomer. Thepolymerization reaction is preferably conducted according to the slurrymethod employing an inert hydrocarbon diluent or liquid propylene as thevehicle. The polymerization temperature can be in the range of about 50°C. to about 100° C. and is preferably at a range or about 60° C. toabout 80° C. Polymerization pressure can also vary over a wide range andis not particularly limited. The polymerization pressure can for examplebe in the range from between atmospheric pressure to 37,000 KPa. Suchprocedures and components are only illustrative of the knowledge in theart with respect to polypropylene polymerization, any are contemplatedas useful within the scope of the invention. For general review ofliterature and patents in the art see “Olefin Polymers (Polypropylene)”in the Kirk-Othiner Encyclopedia of Chemical Technology, 3rd Edition v.16, 453-469 (J. Wiley & Sons, 1981).

The maleinization of the polypropylene compound to maleatedpolypropylene is conveniently accomplished by heating a blend ofpolypropylene and ethylenically unsaturated carboxyl group-containingcompounds, e.g., maleic anhydride, within a range of about 150° to 400°C., often in the presence of free-radical initiators such as organicperoxides that are well-known in the art. Free-radical grafting of thecarboxyl group-containing compounds onto the polypropylene readilyresults. Methods of preparing these grafted polymers are well-known inthe art as illustrated, inter alia, in U.S. Pat. Nos. 3,480,580,3,481,910, 3,577,365, 3,862,265, 4,506,056, and 3,414,551 thedisclosures of which are incorporated herein by reference. Suchprocesses are well-known in the art, for example, an independent sourceof the description of the process is found in Y. Minoura, M. Ueda, S.Mizinuma and M. Oba, 3. Applied Polymer Sci. 1625 (1969). The use ofheat and/or physical shearing optionally with the free-radicalinitiators, in such equipment as extruders, masticators, and the like,to simultaneously accomplish controlled degradation in molecular weightof the polypropylene along with the free-radical grafting of the maleicanhydride, as is known in the art, will be useful in accordance withthis invention.

In particular, it is preferable to conduct the maleinization with suchamounts of maleic anhydride and free-radical initiators, and underconditions of temperature and shearing such that free-radical sites onthe polypropylene are formed substantially at the time of scission ofthe polypropylene chains and are formed at the point of such scission.The maleic anhydride is then grafted onto the scissioned end of one sideof such broken chains. In this manner the anhydride groups are locatedprincipally at the ends of the maleated polypropylene chains, and thesubstantial majority of such maleated polypropylene chains contain onesite of maleinization. This procedure permits grafting of the maleatedpolypropylene at its maleated end to the maleated block copolymer thoughthe use of a difunctional linking or grafting agents having twofunctional groups each functional group being reactive with a maleategroup on the polypropylene and block copolymer. Multiple sites ofmaleinization can lead to grafting of the maleated polypropylene to morethan one maleated block copolymer polymer chain or at more than one siteof one or more maleated block copolymer. The same substantial chemistryapplies to the centipede polymers of the present invention.

In accordance with the above, the free-radical initiator is preferablyused and will typically be utilized in an amount of from about 0.01 to1.0 wt. %, preferably from about 0.02 to 0.5 wt. %, and most preferablyfrom about 0.04 to 0.3 wt. % of the total polypropylene, and solvent ifused, and will be added first. The mixture is then heated to atemperature at or about the known decomposition temperature of theselected free-radical initiator, concurrently with any optionalmechanical shearing. The maleic anhydride is subsequently added in anamount typically from about 0.01 to 10.0 wt. %, preferably from about0.1 to 5 wt. %, and most preferably about 0.75 to 2 wt. % of the totalpolypropylene.

The maleated polypropylene of this invention contain from about 0.01 wt.% incorporated maleic anhydride, based upon the weight of the maleatedpolypropylene, up to about 5 wt. %. Preferably the maleic anhydridecontent will be from about 0.01 to about 2 wt. %, most preferably about0.03 to about 0.2 wt. %. As will be apparent, unreacted polypropylenewill also be present in the reaction mix as will minor amounts ofreaction by-products, such as decomposed free-radical initiatorcompounds and low molecular weight free-radical products. Theseby-products are substantially removed, by methods known in the art,e.g., sparging with nitrogen or washing with water. Maleic anhydride maynot be left in substantial amounts in the polymer without detrimentalaffects on the subsequent reaction of the poly(maleimide-co-alkenylbenzene) with the maleated polypropylene.

The poly(alkenyl benzene-co-maleimide) of the present invention isformed by reacting a poly[alkenylbenzene-(co)-(maleic anhydride)] atfrom about 100° C. to about 250° C. and from about slightly above vacuumto about 20 atmospheres, under substantially dry conditions in thepresence of a primary amine. The present invention is preferablydirected to a polymer compositions of a poly(styrene-co-maleimide)formed by reacting a poly(styrene-co-maleic anhydride) with a primaryamine.

For the purposes of this invention, poly(alkenyl benzene-co-maleimide)and poly(alkyl benzene-co-maleic anhydride) are defined to encompassrandom and stereo-specific copolymers, including copolymers havingalternating alkenyl benzene and maleimide or maleic anhydridecontributed monomer units along the polymer backbone. Such alternatingstructure are typically described as poly(alkenyl benzene-alt-maleimide)and poly(alkyl benzene-alt-maleic anhydride); however, these polymersare encompassed herein within the descriptions poly(alkenylbenzene-co-maleimide) and poly(alkyl benzene-co-maleic anhydride).

Processes for forming poly(alkyl benzene-co-maleic anhydride) polymersare well known to those skilled in the art. The preparation of thecopolymers from electron donor monomers, such as styrene, and electronacceptor monomers, such as maleic anhydride, as a result of complexationof the electron acceptor monomers may be carried out in the absence aswell as in the presence of an organic free radical initiator in bulk, orin an inert hydrocarbon or halogenated hydrocarbon solvent such asbenzene, toluene, hexane, carbon tetrachloride, chloroform, etc. (N. G.Gaylord and H. Antropiusova, Journal of Polymer Science, Part B, 7, 145(1969) and Macromolecules, 2, 442 (1969); A. Takahashi and N. G.Gaylord, Journal of Macromolecular Science (Chemistry), A4, 127 (1970).

Poly(alkyl benzene-co-maleic anhydride) polymers are prepared byreacting monomers of alkenylbenzene with maleic anhydride. The preferredalkenyl benzene monomers used for forming the poly(alkylbenzene-co-maleic anhydride) polymer are styrene or α-methylstyrene.Suitable, but less preferred substitutes are: p-methylstyrene,4-phenylstyrene, m-methylstyrene, o-methylstyrene, p-tert-butylstyrene,dimethylstyrene, and combinations thereof.

The poly(alkyl benzene-co-maleic anhydride) for use in the presentinvention is a polymer containing from about 5 to 99 mole percent ofmaleic anhydride monomer with the remainder being alkyl benzene monomer.The preferred poly(alkyl benzene-co-maleic anhydride) contains from 20to 50 mole percent of maleic anhydride monomer. The most preferredpoly(alkyl benzene-co-maleic anhydride) for use in the present inventionis poly(styrene-co-maleic anhydride) containing 50 mole percent ofmaleic anhydride monomer and 50 mole percent of styrene monomer. Thecomonomers, maleic anhydride and alkenyl benzene, can be randomly oralternatingly distributed in the chain, however, it is preferred to havethese comonomers alternating along the polymer backbone chain.

The poly(alkenyl benzene-co-maleic anhydride) has a molecular weightrange between about 1,000 and up to about 500,000 or higher, moretypically between about 10,000 and 500,000, and even more typicallybetween about 150,000 and 450,000, where the molecular weight isweight-average (“M_(w)”).

The poly(alkenyl benzene-co-maleimide) of the present invention isformed by reacting a poly(alkyl benzene-co-maleic anhydride) in thepresence of a mono-primary amine at a temperature from about 100° C. toabout 300° C. and at a pressure from about slightly above vacuum toabout 20 atmospheres, under substantially dry conditions. The reactantsare preferably dry mixed in the absence of solvents in a suitable mixingapparatus such as a Brabender mixer. It is preferable to purge the mixerwith nitrogen prior to the charging of the reactants. The primary aminemay be added in a singular charge or in sequential partial charges intothe mixer containing a charge of poly(alkyl benzene-co-maleicanhydride). Preferably the primary amine is charged in ratio between 0.8to 1.0 of moles of amine per monomer contributed units of maleicanhydride in the poly(alkyl benzene-co-maleic anhydride).

Suitable primary amine include but are not limited to: alkyl amines;alkyl benzyl amines; alkyl phenyl amines; alkoxybenzyl amines; alkylaminobenzoates; alkoxy aniline; and other linear primary aminescontaining from 1 to 50 carbon atoms, preferably 6 to 30 carbon atoms,in the alkyl and alkoxy substituents in these primary amines. It isunderstood that the alkyl and alkoxy substituents on the above discussedprimary amines can be linear or branched, preferably linear, andsaturated or unsaturated, preferably saturated. Exemplary, but notexclusive of such amines are: hexylamine, octylamine, dodecylamine andthe like.

The poly(alkenyl benzene-co-maleimide), prior to grafting with maleatedpolypropylene, preferably has a molecular weight range between about1,000 and up to about 500,000 or higher, more typically between about10,000 and 500,000, and even more typically between about 150,000 and450,000, where the molecular weight is weight-average (“M_(w)”).

The centipede polymer of the present invention may be prepared by anymeans well known in the art for combining such ingredients, such asblending, milling or internal batch mixing. A rapid and convenientmethod of preparation comprises heating a mixture of the components to atemperature of about 50° C. to about 290° C.

The centipede polymers of this invention are preferably manufactured bymixing and dynamically heat-treating the components described above,namely, by melt-mixing. As for the mixing equipment, any conventional,generally known equipment such as an open-type mixing roll, closed-typeBanbury mixer, closed type Brabender mixer, extruding machine, kneader,continuous mixer, etc., is acceptable. The closed-type Brabender mixeris preferable, and mixing in an inactive gas environment, such asnitrogen or carbon dioxide, is also preferable.

Grafting of maleated polypropylene and poly(alkenylbenzene-co-maleimide) is performed by addition of a grafting agent suchas a polyamine, preferably an organic diamine, to a blend of maleatedpolypropylene and poly(alkenyl benzene-co-maleimide) to partiallycross-link the polypropylene to the poly(alkenyl benzene-co-maleimide)through the maleate functional groups.

Suitable organic diamines or diamine mixtures containing twoaliphatically or cycloaliphatically bound primary amino groups are usedas grafting agents for the process according to the present invention.Such diamines include, for example, aliphatic or cycloaliphatic diaminescorresponding to the following general formula: R₁(NH₂)₂ wherein R₁represents an aliphatic hydrocarbon group having from 2 to 20 carbonatoms, a cycloaliphatic hydrocarbon group having from 4 to 20 carbonatoms, or an aromatic hydrocarbon group having from 6 to 20 carbon atomsor R₁ represents an N-heterocyclic ring having from 4 to 20 carbonatoms, e.g., ethylene diamine; 1,2- and 1,3-propylene diamine;1,4-diaminobutane; 2,2-dimethyl-1,3-diaminopropane; 1,6-diaminohexane;2,5-dimethyl-2,5-diaminohexane;1,6-diamino-2,2,4-trimethyldiaminohexane; 1,8-diaminooctane;1,10-diaminodecane; 1,11-diaminoundecane; 1,12-diaminododecane;1-methyl4-(aminoisopropyl)-cyclohexylamine;3-aminomethyl-3,5,5-trimethyl-cyclohexylamine;1,2-bis-(aminomethyl)-cyclobutane; 1,2-diamino-3,6 dimethylbenzene; 1,2-and 1,4-diaminocyclohexane; 1,2-; 1,4-; 1,5- and 1,8-diaminodecalin;1-methyl-4-aminoisopropyl-cyclohexylamine; 4,4′-diamino-dicyclohexyl;4,4′-diamino-dicyclohexyl methane;2,2′-(bis-4-amino-cyclohexyl)-propane;3,3′-dimethyl-4,4′-diamino-dicyclohexyl methane;1,2-bis-(4-aminocyclohexyl)-ethane;3,3′,5,5′-tetramethyl-bis-(4-aminocyclohexyl)-methane and -propane;1,4-bis-(2-aminoethyl)-benzene; benzidine; 4,4′-thiodianiline,3,3′-dimethoxybenzidine; 2,4-diaminotoluene, diaminoditolylsulfone;2,6-diaminopyridine; 4-methoxy-6-methyl-m-phenylenediamine;diaminodiphenyl ether, 4,4′-bis(o-toluidine); o-phenylenediarnine;o-phenylenediamine, methylenebis(o-chloroaniline);bis(3,4-diaminophenyl)sulfone; diaminodiphenylsulfone;4-chloro-o-phenylenediamine; o-amino-benzylamine; m-phenylenediamine;4,4′-C₁-C₆-dianiline such as 4,4′-methylenedianiline;aniline-formaldehyde resin; and trimethylene glycol di-p-aminobenzoate.Mixtures of these diamines may also be used.

Other suitable polyamines for use as grafting agents in the processaccording to the present invention include bis-(aminoalkyl)-amines,preferably those having a total of from 4 to 12 carbon atoms, e.g.,bis-(2-aminoethyl)-amine, bis-(3-aminopropyl)-amine,bis-(4-aminobutyl)-amine and bis-(6-aminohexyl)-amine, and isomericmixtures of dipropylene triamine and dibutylene triamine. Hexamethylenediamine, tetramethylene diamine, and especially 1,12-diaminododecane arepreferably used.

Thus in the preferred embodiment the process for preparing the graftedpolymer of this invention comprises the steps of:

(A) combining a commercially available poly[alkenylbenzene-(co)-(maleicanhydride)] and a primary amine under substantially dry conditionssufficient to react substantially most of the acid anhydride moieties toform the poly(alkenyl benzeneco-maleimide); and,

(B) mixing a commercially available maleated polypropylene with the massof step (A) under substantially dry conditions of elevated temperature;

(C) adding a diamine to the reaction mass of step (B), under a conditionof agitation sufficient to form the grafted polymer of the presentinvention and cooling; and,

(D) adding an extender oil to the final polymer of step (C) underconditions of agitation.

In broadest terms the process for preparing the grafted polymer of thisinvention comprises combining the poly(alkenyl benzene-co-maleimide)with the maleated polypropylene and the grafting agent under conditionssufficient to permit grafting of at least a minor portion of thepoly(alkenyl benzene-co-maleimide) onto the polypropylene. Thus thegrafted centipede polymer composition of this invention will comprisethe reaction product of the above described, the poly(alkenylbenzene-co-maleimide) grafting agent and the maleated polypropylene. Thegrafting reaction is accomplished by contacting the grafting agent andthe poly(alkenyl benzene-co-maleimide) with the maleated polypropylenewhereupon interaction and cross linking take place. Apparently theprimary amino groups of the grafting agent react to form covalentchemical bonds (imide bonds) with the maleic moieties of the maleatedpolypropylene and the poly(alkenyl benzene-co-maleimide). Thepolypropylene is thus grafted to the poly(alkenyl benzene-co-maleimide)through covalent chemical functional linkages.

For best results, a proportion of approximately one-half molarequivalent of grafting agent per molar equivalent of maleic moiety canbe employed due to the difunctionality of the grafting agent. Thecontacting can be accomplished by combining solutions of the polymericreactants in suitable solvents, such as benzene, toluene, and otherinert organic and inorganic solvents, in a suitable reaction vesselunder substantially anhydrous conditions. Heating will accelerate thereaction and is generally preferred. More preferably commercially, thecontacting can-be accomplished by premixing preformed pellets of theneat functionalized polymers and adding the grafting agent and meltprocessing in a physical blender or mixer, such as a Brabender mixer oran extruder, at temperatures of from about ambient to about 350° C.,preferably about 75° to about 300° C., and most preferably 120° C. toabout 250° C. It is important that essentially all moisture or water beremoved by drying prior to contacting the polymer reactants in order toavoid hydrolysis reactions which will compete with the sought crosslinking and reduce the yield of the grafted copolymer composition ofthis invention.

The amounts of poly(alkenyl benzene-co-maleimide) and maleatedpolypropylene reacted into the grafted compositions of the invention mayvary somewhat depending upon the properties desired in the finishedcomposition. In general, the amounts of maleated polypropylene includedin the grafted composition may range from about 1 to about 50 percent byweight based on total weight of composition. Preferred amounts ofmaleated polypropylene are from 1 to 30 percent by weight with aparticularly preferred amount being from 10 to 25 percent by weight. Theamounts of poly(alkenyl benzene-co-maleimide) centipede polymer includedin the grafted composition may range from about 99 to about 50 percentby weight based on total weight of composition. Preferred amounts of thecentipede polymer are from 99 to 70 percent by weight with aparticularly preferred amount being from 90 to 75 percent by weight.

The centipede polymer gels of the present invention have an extenderadded to the prepared grafted copolymers during final processing.Suitable extenders include extender oils and low molecular weightcompounds or components. Suitable extender oils include those well knownin the art such as naphthenic, aromatic and paraffinic petroleum oilsand silicone oils.

Examples of low molecular weight organic compounds or components usefulas extenders in the compositions of the present invention are lowmolecular weight organic materials having a number-average molecularweight of less than 20,000, preferable less than 10,000, and mostpreferably less than 5,000. Although there is no particular limitationto the material which may be employed, the following is a list ofexamples of appropriate materials:

(1) Softening agents, namely aromatic naphthenic and paraffinicsoftening agents for rubbers or resins;

(2) Plasticizers, namely plasticizers composed of esters includingphthalic, mixed phthalic, aliphatic dibasic acid, glycol, fatty acid,phosphoric and stearic esters, epoxy plasticizers, other plasticizersfor plastics, and phthalate, adipate, sebacate, phosphate, polyether andpolyester plasticizers for NBR;

(3) Tackifiers, namely coumarone resins, coumarone-indene resins,terpene phenol resins, petroleum hydrocarbons and rosin derivative;

(4) Oligomers, namely crown ether, flourine-containing oligomers,polybutenes, xylene resins, chlorinated rubber, polyethylene wax,petroleum resins, rosin ester rubber, polyalkylene glycol diacrylate,liquid rubber (polybutadiene, styrenetbutadiene rubber,butadiene-acrylonitrile rubber, polychloroprene, etc.), siliconeoligomers, and poly-α-olefins;

(5) Lubricants, namely hydrocarbon lubricants such as paraffin and wax,fatty acid lubricants such as higher fatty acid and hydroxy-fatty acid,fatty acid amide lubricants such as fatty acid amide andalkylene-bis-fatty acid amide, ester lubricants such as fatty acid-loweralcohol ester, fatty acid-polyhydric alcohol ester and fattyacid-polyglycol ester, alcoholic lubricants such as fatty alcohol,polyhydric alcohol, polyglycol and polyglycerol, metallic soaps, andmixed lubricants; and,

(6) Petroleum hydrocarbons, namely synthetic terpene resins, aromatichydrocarbon resins, aliphatic hydrocarbon resins, aliphatic cyclichydrocarbon resins, aliphatic or alicyclic petroleum resins, aliphaticor aromatic petroleum resins, polymers of unsaturated hydrocarbons, andhydrogenated hydrocarbon resins.

Other appropriate low-molecular weight organic materials includelatexes, emulsions, liquid crystals, bituminous compositions, andphosphazenes. One or more of these materials may be used as extenders.

In accordance with the present invention, the grafted polymer containinggel composition of the present invention may have added thereto at leastabout 1, preferably 30 to 1,000, parts by weight of extender per 100parts by weight of the grafted copolymers. Most preferred amounts ofadded extender include from about 50 to about 500 parts of oil per 100parts of grafted copolymer and ideally about 80 to about 300 parts ofextender per 100 parts of grafted copolymer. The weight percent ratio ofthe polyalkylene grafted poly(alkenyl benzene-co-maleimide) to theextender is from about 100:1 to about 1:100, preferably 5:1 to about1:5.

The polymer gels produced according to the present invention generallyhave high damping properties having a tan δ in the range of about 0.1 toabout 1.0, preferably higher than 0.3 over the temperature range of 30°C. to 100° C., and a Shore A hardness ranging from 0 to about 50,preferably about 0 to about 30, most preferably about 5 to 20 at about20° C. to 25° C. or at room temperature. The service temperature of thegels of the present invention is less than or equal to 100° C. for mostof the polymers of the present invention, e.g., 100° C. compression setof the gel is about 50. Some of the extended polymers of the presentinvention have a potential use up to 140° C.

It is frequently desirable to include other additives well known in therubber art to the compositions of the present application. Stabilizers,antioxidants, conventional fillers, reinforcing agents, reinforcingresins, pigments, fragrances and the like are examples of some suchadditives. Specific examples of useful antioxidants and stabilizersinclude 2-(2′-hydroxy-5′-methylphenyl) benzotriazole, nickeldibutyldithiocarbamate, zinc dibutyl dithiocarbamate, tris(nonylphenyl)phosphite, 2,6-di-t-butyl-4-methylphenol and the like. Exemplaryconventional fillers and pigments include silica, carbon black, titaniumdioxide, iron oxide and the like. These compounding ingredients areincorporated in suitable amounts depending upon the contemplated use ofthe product, preferably in the range of 1 to 350 parts of additives orcompounding ingredients per 100 parts of grafted copolymer.

A reinforcement may be defined as the material that is added to aresinous matrix to improve the strength of the polymer. Most of thesereinforcing materials are inorganic or organic products of highmolecular weight. Various examples include glass fibers, asbestos, boronfibers, carbon and graphite fibers, whiskers, quartz and silica fibers,ceramic fibers, metal fibers, natural organic fibers, and syntheticorganic fibers. Other elastomers and resins are also useful to enhancespecific properties like damping properties, adhesion andprocessability. Examples of other elastomers and resins includeadhesive-like products including Reostomer (produced by Riken- VinylInc.), hydrogenated polystyrene-(medium or high 3,4)polyisoprene-polystyrene block copolymers such as Hybler (produced byKurare Inc.), polynorbornenes such as Norsorex (produced by Nippon ZeonInc.) and the like. In this case the foregoing materials are equallyapplicable to the present centipede polymer compositions.

The gels containing oil or low molecular weight component extended andpolypropylene compositions of the present invention may be prepared byany means well known in the art for combining such ingredients, such assolution blending, milling, internal batch mixing, or continuousextrusion of a solid form of the centipede polymer and polypropylenecompositions and the other ingredients. A rapid and convenient method ofpreparation comprises heating a mixture of the components to atemperature of about 50° C. to about 290° C.

The gels containing oil extended grafted poly(alkenylbenzene-co-maleimide)-polypropylene compositions of the presentinvention can be manufactured by mixing and dynamically heat-treatingthe components described above, namely, by melt-mixing. As for themixing equipment, any conventional, generally known equipment such as anopen-type mixing roll, closed-type Banbury mixer, extruding machine,kneader, continuous mixer, etc., is acceptable. The closed-type ispreferable, and mixing in an inactive gas environment, such as nitrogenor argon, is also preferable.

The composition obtained using the manufacturing method of thisinvention can be molded with equipment conventionally used for moldingthermoplastics. It is suitable for extrusion molding, calendar molding,and particularly injection molding.

The composition of the present invention can be mixed in anyconventional mixer such as a Banbury mixer or roll mill or extrudernormally conducted within the temperature range of about 120° C. toabout 300° C., preferably maintaining the composition above its meltingpoint for a few minutes up to several hours, preferably 10 to 40minutes. A particularly useful technique is to add any fillers in thebeginning of the mixing cycle in order to take maximum advantage ofheating time and to prevent surface bleeding and overheating whenforming the molded articles.

The resultant gel composition may be molded in appropriate press ovensand the like to form products in the form of extruded pellets, cutdices, preferably as small as possible since smaller pellets provideshort heating times and better flow when utilized in flow molding.Ground pellets may also be utilized.

The extended grafted centipede polymers of the present invention can beused in high temperature applications including uses in injectionmolding or in any other compositions typically used for elastomericproperties.

In summary, the molded polymers produced from the gels containingextended grafted poly(alkenyl benzene-co-maleimide) and polypropylenecompositions of the present invention retain elastomeric characteristicsand are useful in high temperature applications and/or high dampingapplications.

Damping is the absorption of mechanical energy by a material in contactwith the source of that energy. It is desirable to damp or mitigate thetransmission of mechanical energy from, e.g., a motor, engine, or powersource, to its surroundings. Elastomeric materials are often used forthis purpose. It is desirable that such materials be highly effective inconverting this mechanical energy into heat rather than transmitting itto the surroundings. It is further desirable that this damping orconversion is effective over a wide range of temperatures andfrequencies commonly found near motors, automobiles, trucks, trains,planes, and the like.

A convenient measurement of damping is the determination of a parametercalled tan δ. A forced oscillation is applied to a material at frequencyf and the transmitted force and phase shift are measured. The phaseshift angle delta is recorded. The value of tan δ is proportional to theratio of (energy dissipated)/(energy stored). The measurement can bemade by any of several commercial testing devices, and may be made by asweep of frequencies at a fixed temperature, then repeating that sweepat several other temperatures, followed by the development of a mastercurve of tan δ vs. frequency by curve alignment. An alternate method isto measure tan δ at constant frequency (such as at 10 hz) over atemperature range. We have defined a thermoplastic unfilled material asuseful for damping when tan δ>˜0.3 over at least a 4 decade range,preferably a 6 decade range of frequency.

It is further important that this high degree of absorption of energy beaccompanied by good mechanical and thermal stability, as the partprepared from the subject polymers will be cycled through variousenvironments and repeatedly such to various forces of compression,tension, bending, and the like.

The compositions of the present invention are favorably used in themanufacturing of any product in which the following properties areadvantageous: a high degree of softness, heat resistance, decentmechanical properties, elasticity and/or high damping. The compositionsof the present invention can be used in all industry fields, inparticular, in the fabrication of automotive parts, tire tread rubbers,household electrical appliances, industrial machinery, precisioninstruments, transport machinery, constructions, engineering, andmedical instruments.

Representative examples of the use of the extended graft polymers of thepresent invention are in the fabrication of damping materials andvibration restraining materials. These uses involve connecting materialssuch as sealing materials, packing, gaskets and grommets, supportingmaterials such as mounts, holders and insulators, and cushion materialssuch as stoppers, cushions, and bumpers. These materials are also usedin equipment producing vibration or noise and household electricalappliances, such as in air-conditioners, laundry machines,refrigerators, electric fans, vacuums, driers, printers and ventilatorfans. Further, these materials are also suitable for impact absorbingmaterials in audio equipment and electronic or electrical equipment,sporting goods and shoes. Further, as super low hardness rubbers, thesematerials are applicable for use in appliances, damping rubbers, and aslow hardness plastics, and it is preferable for molding materials.Further, because the present compositions can be used to control therelease of internal low molecular weight materials out from thecompositions, it is useful as a release support to emit materials suchas fragrance materials, medical materials and other functionalmaterials. The compositions of the present invention also possessutility in applications of use in liquid crystals, adhesive materialsand coating materials.

Specific examples of uses of the compositions of the present inventionas damping materials are as follows:

in audio equipment, such as in insulators for a portable CD or a CDmounted on a vehicle, mike holders for home video cassette recorder,radio cassette recorder, karaoke or handy mike, etc., an edge cone of aspeaker, a tape holder of a radio cassette, a holder of a portablemini-disk player, an optical disk holder of a digital video disk, etc.;

in information relating equipment, such as in insulators for a harddisk, insulators for motors such as a spindle motor for HHD and steppingmotor, insulators for floppy disk drive, insulators for CD-ROM ofpersonal computer, and a holder for optical disk;

in communication equipment, such as in a holder for compact highperformance mike or speaker of a portable telephone, a pocket bell orPHS, a mike holder for a wireless equipment, and a disk holder forportable note type electronic equipment;

in home electronics equipment, such as in insulators for CD-ROM of homeTV game, insulators for cassette holder or CD-ROM of cassette holder orgame machine, a holder of high performance mike, and cone edge ofspeaker; and

in other applications, such as in damping materials for printer head ofa wordprocessor, printer of personal computer, small or middle handytype printer, or name printers, and insulators for CD-ROM used formeasure equipment.

In the following, the present invention will be described in more detailwith reference to non-limitative examples. The following examples andtables are presented for purposes of illustration only and are not to beconstrued in a limiting sense.

EXAMPLE 1 Preparation of the Centipede Polymer

A nitrogen purged Brabender mixer (˜310 gram capacity) equipped with aBanbury blade was initially set to 30 rpm and the temperature was set to80° C. The mixer was then charged with 150 g of poly(styrene-alt-maleicanhydride) (obtained from Aldrich Chemical Company of 1001 West SaintPaul Avenue, Milwaukee, Wis. Catalog Number: 18,293-1, CAS Number:9011-13-6)(M_(n)=350,000) and 96 g of octylamine (obtained from Aldrich,99% purity). After 15 minutes of continuous mixing, the mixture wasallowed to heat up at a rate of ˜4° C./min. Once the temperature reached150° C., agitation was discontinued. When the temperature reached 210°C., the heating element was set at isothermal conditions and agitationwas again resumed at a speed of 70 rpm and mixing was continued for anadditional 60 minutes. The heating element of the mixer was turned off,and the polymer mass within the mixer was permitted to cool down to 160°C. at a rate of ˜4° C./min. The agitation was then stopped and thecentipede polymer product mass was then removed from the mixer.

IR absorption peaks characteristic of the polymer mass were noted at 705cm⁻¹, 1701 cm⁻¹, 1770 cm⁻¹, 2855 cm⁻¹ and 2926 cm⁻¹. The ratio of theintensities was observed at I₂₉₂₆ to I₁₇₀₁≅0.55. T_(g) was estimated tobe at 50° C. The acid value of the polymer was 0.180 meq./gram using theNaOH titration method in a tetrahydrofuran solution.

EXAMPLE 2 Grafting of the Centipede Polymer and Maleated Polypropylene

A nitrogen purged Brabender mixer (˜310 g capacity) equipped with aBanbury blade was initially set to 60 rpm and 195° C. The mixer was thencharged with 36.6 g of commercial maleated poypropylene (from the ExxonChemical Company, trade name Exxelor PO 1015). After 6 minutes, a chargeof 145 g of the centipede polymer product of Example 1 was added to themixer. The polymers were agitated for an additional 10 minutes. A chargeof 1.6 g of dodecane diamine (from Aldrich, purity=98%) was then added,and at the same time the agitation speed was readjusted to 120 rpm.After 6 minutes the torque of the mixer increased and the agitationspeed was again readjusted to 60 rpm. After an addition mixing at 60 rpmfor 8 minutes, the heating element of the mixer was turned off and theagitation speed was again readjusted to 40 rpm. The mixture waspermitted to cool to about 160° C. at a rate of ˜4° C./min. Finally,agitation was discontinued and the grafted polymer product was removedfrom the mixer.

EXAMPLE 3

A charge of 15 g of the grafted polymer product of Example 2 was addedto a Brabender mixer (50 g capacity) equipped with a roller blade. Themixer was initially set to 50° C. and 20 rpm. A charge of 17.7 g ofdi(tridecyl)phthalate (DTDP) oil was slowly added to the contents of themixer. After 5 minutes, the temperature of the mixer was reset to 160°C. and the agitation speed was reset to 70 rpm. After 105 minutes ofcontinuous mixing, another charge of 17.8 g of DTDP oil was added to thecontents of the mixer. The material was then further mixed for 35minutes at 90 rpm. The agitation was then discontinued and the productwas removed from the mixer.

EXAMPLE 4

A charge of 15 g of the grafted polymer product of Example 2 was addedto a Brabender mixer (50 g capacity) equipped with a roller blade. Themixer was initially set to 80° C. and 20 rpm. A charge of 17.7 g of DTDPoil was slowly added to the contents of the mixer. After 8 minutes, thetemperature of the mixer was reset to 160° C. amd the agitation speedwas reset to 90 rpm. After 12 minutes an additional two grams of thegrafted polymer product of Example 2 was added to the contents of themixer. After 108 minutes of continuous mixing, a charge of 17.8 g oftrioctyl phosphate (TOP) oil was added to the contents of the mixer. Thematerial was then further mixed for 195 minutes at 90 rpm. The agitationwas then discontinued and the product was removed from the mixer.

The products were thereafter molded into sheets and cylinder buttons at˜155° C. Ring samples were cut from these sheet for tensilemeasurements. The details of their physical properties are listed in thefollowing Table 1:

TABLE 1 PP/ Shore A Example Polymer Oil Type Centipede-C₈ C.S.¹ Tb/EbTan δ hardness No. used (weight %) (wt. ratio) (100° C.) (psi/%) (−10,20, 45° C.) (25° C.) 3 Example 2 DTDP 20/80 87.8 — 0.78, 0.60, 0.58 0-2(70%) 4 Example 2 DTDP-TOP 20/80 65.4 21/193 0.54, 0.51, 0.45 0-2 (67%)¹The Compression Set (C.S.) was measured based on conditions of ASTMD395-89, except that the sample size and displacement were changed asfollows: Sample height - 0.5 inches; Sample diameter - 0.55 inches;Displacement - Sample is compressed to 0.375 inches and stored in anoven at 100° C. (or at 150° C. in subsequent examples) for 22 hours. Thesample is removed from the oven, the stress on the sample is relieved, #the sample is stored at room temperature for 30 minutes and the recoveryof the sample is measured as the final sample height as X in:Compression Set = ((0.5 - X)/(0.5-0.375)) × 100%.

We claim:
 1. A centipede polymer gel composition, comprising: apolyalkylene grafted poly(alkenyl benzene-co-maleimide) comprising fromabout 50 wt % to about 99 wt % of a poly(alkenyl benzene-co-maleimide)and about 1 wt % to about 50 wt % of a maleated polyalkylene and fromabout 0.01 to about 10 wt % of a diamine, and an extender in an amountsufficient to form a gel.
 2. The centipede polymer gel composition ofclaim 1 wherein the weight percent ratio said polyalkylene graftedpoly(alkenyl benzene-co-maleimide) to said extender is from about 100:1to about 1:100.
 3. The centipede polymer gel composition of claim 1,wherein the monomer for forming the alkenyl benzene moiety of saidpoly(alkenyl benzene-co-maleimide) is selected from the group consistingof: styrene, α-methylstyrene, p-methylstyrene, 4-phenlstyrene,m-methylstyrene, o-methylstyrene, p-tert-dimethylstyrene, and mixturesthereof.
 4. The centipede polymer gel composition of claim 1, whereinthe monomer for forming the alkylene moiety of said maleatedpolyalkylene is selected from the goup consisting of ethylene, propyleneand combinations thereof.
 5. The centipede polymer gel composition ofclaim 1, wherein said diamine is selected from the group consisting of:ethylene diamine; 1,2- and 1,3-propylene diamine; 1,4-diaminobutane;2,2-dimethyl-1,3-diaminopropane; 1,6-diaminohexane;2,5-dimethyl-2,5-diaminohexane;1,6-diamino-2,2,4-trimethyldiaminohexane; 1,8-diaminooctane;1,10-diaminodecane; 1,11-diaminoundecane; 1,12-diaminododecane;1-methyl-4-(aminoisopropyl)-cyclohexylamine;3-aminomethyl-3,5,5-trimethyl-cyclohexylamine;1,2-bis-(aminomethyl)-cyclobutane; 1,2-diamino-3,6-dimethylbenzene; 1,2-and 1,4-diaminocyclohexane; 1,2-; 1,4-; 1,5- and 1,8-diaminodecalin;1-methyl-4-aminoisopropyl-cyclohexylamine; 4,4′-diamino-dicyclohexyl;4,4′-diamino-dicyclohexyl methane;2,2′-(bis-4-amino-cyclohexyl)-propane;3,3′-dimethyl-4,4′-diamino-dicyclohexyl methane;1,2-bis-(4-aminocyclohexyl)-ethane;3,3′,5,5′-tetramethyl-bis-(4-aminocyclohexyl)-methane and -propane;1,4-bis-(2-aminoethyl)-benzene; benzidine; 4,4′-thiodianiline,3,3′-dimethoxybenzidine; 2,4-diaminotoluene, diaminoditolylsulfone;2,6-diaminopyridine; 4-methoxy-6-methyl-m-phenylenediamine;diaminodiphenyl ether; 4,4′-bis(o-toluidine); o-phenylenediamine;o-phenylenediamine, methylenebis(o-chloroaniline);bis(3,4-diaminophenyl)sulfone; diaminodiphenylsulfone;4-chloro-o-phenylenediamine; m-aminobenzylamine; m-phenylenediamine;4,4′-C₁-C₆-dianiline such as 4,4′-methylenedianiline;aniline-formaldehyde resin; trimethylene glycol di-p-aminobenzoate;bis-(2-aminoethyl)-amine, bis-(3-aminopropyl)-alnine,bis-(4-aminobutyl)-amine; bis-(6-aminohexyl)-amine, isomeric mixtures ofdipropylene triamine and dibutylene triamine; and mixtures thereof. 6.The centipede polymer gel composition of claim 1, wherein the gel hasdamaging properties having a tan δ in the range of about 1 to about 0.10over the temperature range of −10° C. to 100° C.
 7. The centipedepolymer gel composition of claim 1, wherein the gel has a Shore Ahardness ranging from about 0 to about 50 at about 20° C. to 25° C. 8.The centipede polymer gel composition of claim 1, wherein the gel has aShore A hardness ranging from about 0 to 30 at about 20°°C. to 25°°C. 9.The centipede polymer gel composition of claim 1, further comprisingfrom 1 to 350 parts of a inorganic filler, additive or compoundingingredient based on 100 parts by weight of the grafted copolymercomposition component.
 10. The centipede polymer gel composition ofclaim 1, wherein the extender is at least one compound selected from thegroup consisting of: softening agents, plasticizers, tackifiers,oligomers, lubricants, petroleum hydrocarbons, silicone oil, aromaticoil, naphthenic oil and paraffinic oil.
 11. A centipede polymercomposition, comprising: a polyalkylene grafted poly(alkenylbenzene-co-maleimide) comprising from about 50 wt % to about 99 wt % ofa poly(alkenyl benzene-co-maleimide) and about 1 wt % to about 50 wt %of a maleated polyalkylene and from about 0.1 to about 10 wt % of adiamine, and wherein the maleimide contributed monomer units of thepoly(alkenyl benzene-co-maleimide) is formed by the reaction of maleicanhydride and a primary amine.
 12. The polymer composition of claim 11wherein the primary amine is selected from the group consisting of:alkyl amines, alkyl benzyl amines; alkyl phenyl amines; alkoxybenzylamines; alkyl aminobenzoates; and alkoxy aniline; containing from 1 to50 carbon atoms in the alkyl and alkoxy substituents.
 13. The polymercomposition of claim 11 wherein said maleated polyalkylene comprises aweight average Mw of between about 10,000 to about 10,000.000.
 14. Thepolymer composition of claim 11 wherein said maleated polyalkylene issubstantially crystalline.
 15. The polymer composition of claim 11wherein said maleated polyalkylene includes ehtylene and propylenesegments.
 16. The polymer composition of claim 11 wherein thepoly(alkenyl benzene-co-maleimide) has a weight average molecular weightbetween about 10,000 and 500,000.
 17. The polymer composition of claim11 wherein said poly(alkenyl benzene-co-maleimide) includes from about20 to 50 mole percent maleic anhydride monomers.
 18. A centipede polmercomposition, comprising: a polyalkylene grafted poly(alkenylbenzene-co-maleimide) comprising from about 50 wt % to about 99 wt % ofa poly(alkenyl benzene-co-maleimide) and about 1 wt % to about 50 wt %of a maleated polyalkylene and from about 0.1 to about 10 wt % of adiamine selected from the group consisting of: aliphatic orcycloaliphatic diamines corresponding to the following general formula:R₁(NH₂)₂ wherein R₁ represents an aliphatic hydrocarbon group havingfrom 2 to 20 carbon atoms, a cycloaliphatic hydrocarbon group havingfrom 4 to 20 carbon atoms, or an aromatic hydrocarbon group having from6 to 20 carbon atoms or R₁ represents an N-heterocyclic ring having from4 to 20 carbon atoms.
 19. The centipede polymer gel composition of claim18, wherein said diamine is selected from the group consisting of:ethylene diamine; 1,2- and 1,3-propylene diamine; 1,4-diaminobutane;2,2-dimethyl-1,3-diaminopropane; 1,6-diaminohexane;2,5-dimethyl-2,5-diaminohexane;1,6-diamino-2,2,4-trimethyldiaminohexane; 1,8-diaminooctane;1,10-diaminodecane; 1,11-diaminoundecane; 1,12-diaminododecane;1-methyl-4-(aminoisopropyl)-cyclohexylamine;3-aminomethyl-3,5,5-trimethyl-cyclohexylamine;1,2-bis-(aminomethyl)-cyclobutane; 1,2-diamino-3,6-dimethylbenzene; 1,2-and 1,4-diaminocyclohexane; 1,2-; 1,4-; 1,5- and 1,8-diaminodecalin;1-methyl-4-aminoisopropyl-cyclohexylamine; 4,4′-diamino-dicyclohexyl;4,4′-diamino-dicyclohexyl methane;2,2′-(bis-4-amino-cyclohexyl)-propane;3,3′-dimethyl-4,4′-diamino-dicyclohexyl methane;1,2-bis-(4-aminocyclohexyl)-ethane;3,3′,5,5′-tetramethyl-bis-(4-aminocyclohexyl)-methane and -propane;1,4-bis-(2-aminoethyl)-benzene; benzidine; 4,4′-thiodianiline,3,3′-dimethoxybenzidine; 2,4-diaminotoluene, diaminoditolylsulfone;2,6-diaminopyridine; 4-methoxy-6-methyl-m-phenylenediamine;diaminodiphenyl ether; 4,4′-bis(o-toluidine); o-phenylenediamine;o-phenylenediamine, methylenebis(o-chloroaniline);bis(3,4-diaminophenyl)sulfone; diaminodiphenylsulfone;4-chloro-o-phenylenediamine; m-aminobenzylamine;m-phenylenediamine;amines; 4,4′-C₁-C₆-dianiline such as4,4′-methylenedianiline; aniline-formaldehyde resin; trimethylene glycoldi-p-aminobenzoate; bis-(2-aminoethyl)-amine, bis-(3-aminopropyl)-amine,bis-(4-aminobuty)-amine isomeric mixtures of dipropylene triamine anddibutylene triamine; and mixtures thereof.